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Abstract:

Water-based coatings having writable-erasable surfaces are provided. The
coatings have many desirable attributes. For example, the coatings cure
under ambient conditions, have low or no VOC emissions during and upon
curing, and have reduced tendency to form ghost images, even after
prolonged normal use.

Claims:

1.-73. (canceled)

74. A method comprising: combining an isocyanate resin component and an
acrylic polyol resin component with each other to form a composition
comprising 20-40% by weight of the isocyanate component and 10-20% by
weight of the acrylic polyol resin component, which composition cures to
form a material having a write-erasable surface.

75. The method of claim 74, wherein the material has at least one
characteristic selected from the group consisting of: a Sward hardness of
greater than about 25; a Taber abrasion of less than 150 mg/thousand
cycles; the elongation at break between about 5 percent and about 400
percent; the sag resistance between about 4 mils to about 24 mils; a
contact angle measured from the surface of the material using deionized
water of less than about 150 degree; and combination thereof

76. The method of claim 74, wherein the material is characterized in
that, when its surface is written on with a marking material comprising a
colorant and a solvent, the solvent comprising one or more of water,
alcohols, alkoxy alcohols, ketones, ketonic alcohols, esters, acetates,
mineral spirits, or mixtures thereof, the marking material can be erased
from the surface of the write-erasable material to be substantially
invisible for more than 100 cycles of writing and erasing at the same
position.

77. The method of claim 74, wherein the composition has pot life in a
range of about 10 minutes to about 16 hours.

78. The method of claim 74, further comprising a step of applying the
composition to a substrate.

79. The method of claim 78, wherein the step of combining and the step of
applying are performed substantially simultaneously.

80. The method of claim 78, wherein the step of applying comprises
rolling, painting, spraying or any combination thereof.

81. The method of claim 74, further comprising a step of permitting the
composition to cure.

82. The method of claim 74, further comprising a step of writing with a
marking material on the write-erasable surface.

83. The method of claim 81, further comprising a step of erasing the
marking material.

84. The method of claim 74, wherein the step of combining comprises
mixing separate compositions, a first of which comprises the acrylic
polyol resin component and a second of which comprises the isocyanate
component.

85. The method of claim 83, wherein the separate compositions are
maintained in separate containers prior to their combination.

Description:

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation-in-part of PCT Patent
Application Serial No. PCT/US2007/073524, filed on Jul. 13, 2007, the
complete disclosure of which is incorporated by reference herein.

TECHNICAL FIELD

[0002] This disclosure relates to water-based coatings for
writable-erasable surfaces, products that include such coatings, and to
the methods of making the same.

BACKGROUND

[0003] Classroom education has traditionally relied upon a "blackboard"
and chalk as an instruction medium. This technique can be messy, dusty,
and many blackboards cannot be used with all chalk types and colors. The
dust generated can lead to many respiratory afflictions. Overhead
projectors, laptop computers and dry erase boards (often referred to
commonly as "whiteboards") are alternatives to traditional blackboards.

[0004] Dry erase boards typically include a substrate, such as paper or
board, and a coating, such as a lacquer coating, extending upon the
substrate. The coating provides a writing surface that can be marked
using dry erase marking pens. Dry erase marking pens, which are typically
felt tip marking instruments, contain inks that not only can mark such
surfaces, but also can be erased with minimal effort using, e.g., a dry
eraser, cloth, or paper tissue.

[0005] The erasability of dry erase inks from the writing surfaces of dry
erase boards can deteriorate over time, resulting in the formation of
non-removable "ghost images." In addition, such surfaces can be
incompatible with some dry erase markers, and can be permanently marked
if inadvertently written on with a permanent marker.

SUMMARY

[0006] This disclosure relates to coatings having writable-erasable
surfaces, products that include such coatings (e.g., whiteboards), and to
methods of making and using the same. Generally, the coatings having the
writable-erasable surfaces are produced from one or more precursor
materials in a water-based carrier; the coatings cure under ambient
conditions. When the writing surface is marked with a marking material,
such as a water- or alcohol-based marking material, the marking material
can be erased to be substantially invisible with little or no ghosting,
even after prolonged and repeated use. The one or more materials that
form the coatings emit minimal volatile organic compounds (VOCs) during
their application to a substrate or during their curing on the substrate.
The resulting coatings have many desirable attributes, including one or
more of the following: low porosity, low surface roughness, high
elongation at break, high Taber abrasion resistance, and high Sward
hardness. Generally, while not intending to be bound by any theory, it is
believed that the low porosity of the coatings makes the coatings
substantially impervious to the marking materials, while the low surface
roughness prevents the marking materials from becoming entrapped on the
surface beyond effective reach of an eraser.

[0007] In one aspect of the disclosure, a writable-erasable product
includes a cured coating (such as crosslinked) extending upon a substrate
and having a writable-erasable surface. The coating is curable under
ambient conditions, and can be formed from one or more materials, each of
the one or more materials including one or more functional groups
independently selected from G1 and G2, with at least one material of the
one or more materials in a water-based carrier, wherein each G1
functional group is independently selected from among isocyanate,
epoxide, urethane, ethyleneoxy, and ethylene, wherein the ethylene is
optionally substituted with hydroxyl, acetoxy, or alkoxycarbonyl; and
each G2 functional group is independently selected from among hydroxyl,
amine, phenol, carboxylic acid, acid anhydride, aziridine, and thiol.
After the writable-erasable surface is marked with a marking material
including a colorant and a solvent, the solvent including one or more of
water, alcohols, alkoxy alcohols, ketones, ketonic alcohols, esters,
acetates, mineral spirits, or mixtures thereof, the marking material can
be erased from the writable-erasable surface to be substantially
invisible.

[0008] In some implementations, the coating can be formed from one or more
materials, each of the one or more materials including one or more G1
functional groups, with at least one material of the one or more
materials in a water-based carrier.

[0009] In some implementations, the coating can be formed from two or more
materials, wherein a first material includes one or more G1 functional
groups and a second material includes one or more G2 functional groups,
with at least one material of the two or more materials in a water-based
carrier.

[0010] In some implementations, the cured coating and/or the
writable-erasable surface may have one or more of the following
attributes. The coating may have a porosity of less than about 40
percent; a thickness of from about 0.001 inch to about 0.125 inch; a
Taber abrasion value of from about 100 to about 125 mg/thousand cycles; a
Sward hardness of greater than about 10; an elongation at break of
between about 5 percent to about 400 percent; a sag resistance of between
about 4 and about 24; a VOC content of less than about 350 g/L (such as
less than about 50 g/L).

[0012] In some implementations, G1 is ethylene substituted with
alkoxycarbonyl, or ethylene optionally substituted with acetoxy.

[0013] In some implementations, the one or more materials including one or
more G1 groups wherein G1 is ethylene substituted with alkoxycarbonyl,
further includes one or more materials including one or more G1 groups
wherein G1 is ethyleneoxy.

[0014] In some implementations, the one or more materials is a
polyurethane. In such implementations, the one or more materials can
further include a polyacrylate.

[0015] In some implementations, the one or more materials is in the form
of a dispersion.

[0019] In some implementations, the one or more materials including one or
more G1 functional group includes an aliphatic diisocyanate (e.g.,
hexamethylene-1,6-diisocyanate, IPDI and the like) such as an hydrophilic
aliphatic diisocyanate or their oligomers and homopolymers (e.g.,
homopolymer of hexamethylene-1,6-diisocyanate), or their mixtures.

[0020] In some implementations, the one or more materials including one or
more G1 functional group includes a polymeric material.

[0021] In some implementations, the one or more materials including one or
more G2 functional group includes an α,ω-diol.

[0022] In some implementations, the one or more materials including one or
more G2 functional group includes a polymeric material (e.g., an acrylic
polyol or an acrylic based diol).

[0023] The writable-erasable surface can be erased to be substantially
invisible after writing and erasing at the same position for more than
about 100 cycles, or even more than about 5,000 cycles. The
writable-erasable surface can have an average surface roughness (Ra)
of less than about 7,500 nm; a maximum surface roughness (Rm) of
less than about 10,000 nm; a contact angle of greater than about 35
degrees; a contact angle of less than about 150 degrees.

[0024] In some implementations, the substrate can be selected from the
group consisting of cellulosic material, glass, wall (such as plaster or
painted), fiber board (e.g., a whiteboard in which the cured coating can
extend upon a fiber board), particle board (e.g., a chalkboard or
blackboard), gypsum board, wood, densified ceramics, stone (such as
granite), and metal (such as aluminum or stainless steel).

[0025] In some implementations, the substrate can be selected from a
flexible film or a rigid immovable structure.

[0026] In some implementations, the marking material can be erased from
the writable-erasable surface to be substantially invisible by wiping the
marks with an eraser including a fibrous material.

[0028] In some implementations, the writable-erasable product can form a
whiteboard in which the cured coating extends upon a fiberboard; can form
a part of a wall e.g., of a structure; or can form a plurality of sheets,
each sheet including a substrate (e.g., in the form of a paper) having
the cured coating extending thereupon.

[0029] In another aspect, the disclosure describes a method of making a
writable-erasable product, the method including applying a coating to a
substrate, and curing the coating (e.g., under ambient conditions) to
provide a cured coating defining a writable-erasable surface. After the
writable-erasable surface is marked with a marking material, the marking
material can be erased from the writable-erasable surface to be
substantially invisible.

[0030] In such implementations, the coating includes one or more
materials, each of the one or more materials including one or more
functional groups independently selected from G1 and G2, with at least
one material of the one or more materials in a water-based carrier,
wherein each G1 functional group is independently selected from among
isocyanate, epoxide, urethane, ethyleneoxy, and ethylene, wherein the
ethylene is optionally substituted with hydroxyl, acetoxy, or
alkoxycarbonyl; and each G2 functional group is independently selected
from among hydroxyl, amine, phenol, carboxylic acid, acid anhydride,
aziridine, and thiol.

[0031] In such implementations, the marking material includes a colorant
and a solvent (e.g., water, alcohol, alkoxy alcohol, ketone, ketonic
alcohol, ester, acetate, mineral spirit, or their mixtures).

[0032] In some implementations, the coating prior to application has less
than about 350 g/L of VOCs (e.g., less than about 50 g/L of VOCs).

[0033] In some implementations, the coating can be prepared by combining
the one or more materials including one or more G1 functional group
(e.g., an isocyanate), and the one or more materials including one or
more G2 functional group (e.g., an hydroxyl).

[0034] In some implementations, prior to combining, the one or more
materials including one or more G1 functional group (e.g., an isocyanate)
can be in a first container, and the one or more materials including one
or more G2 functional group (e.g., an hydroxyl) can be in a second
container.

[0035] In some implementations, the one or more materials including one or
more G2 functional group (e.g., an hydroxyl) also includes a crosslinking
agent having a functionality of two or greater.

[0036] In some implementations, the one or more materials can be in a
water-based carrier.

[0037] In another aspect, the disclosure describes a method of changeably
presenting information including selecting a writable-erasable product,
marking the writable-erasable surface with a first information with a
marking material. After the surface has been marked with the marking
material, erasing the marking of the first information (e.g., by applying
an eraser to the writable-erasable surface) from the writable-erasable
surface to be substantially invisible; marking the writable-erasable
surface with a different information and erasing the marking of the
different information from the writable-erasable surface to be
substantially invisible.

[0038] In some implementations, the coating can be formed from one or more
materials, each of the one or more materials including one or more
functional groups independently selected from G1 and G2, at least one
material of the one or more materials in a water-based carrier, wherein
each G1 functional group is independently selected from among isocyanate,
epoxide, urethane, ethyleneoxy, and ethylene, wherein the ethylene is
optionally substituted with hydroxyl, acetoxy, or alkoxycarbonyl; and
each G2 functional group is independently selected from among hydroxyl,
amine, phenol, carboxylic acid, acid anhydride, aziridine, and thiol.

[0039] In some implementations, the coating can be formed from one or more
materials including one or more isocyanate groups, one or more materials
including one or more hydroxyl groups, at least one material of the one
or more materials in a water-based carrier.

[0040] In some implementations, the marking material includes a colorant
and a solvent (e.g., water, alcohol, alkoxy alcohol, ketone, ketonic
alcohol, ester, acetate, mineral spirit, or their mixtures).

[0041] In some implementations, the eraser includes a fibrous material.

[0043] In some implementations, the marking and erasing of different
information are performed repeatedly.

[0044] In another aspect, the disclosure describes a composition including
an hydrophilic aliphatic diisocyanate or their homopolymers and
oligomers, an acrylic polyol, water, and optionally an accelerator and/or
an acid promoter.

[0045] In some implementations, the composition can include titanium
dioxide, a surface additive, a wetting agent, a defoaming agent, a
pigment or a colorant.

[0046] In some implementations, the composition can have less than about
350 g/L of VOCs (e.g., less than about 50 g/L of VOCs).

[0047] In another aspect, the disclosure describes a writable-erasable
product including a cured coating extending upon a substrate and having a
writable-erasable surface. The coating can cure under ambient conditions
and can be formed from a material in a water-based carrier. After the
writable-erasable surface is marked with a marking material, including a
colorant and a solvent (e.g., water, alcohol, alkoxy alcohol, ketone,
ketonic alcohol, ester, acetate, mineral spirit, or their mixtures), the
marking material can be erased from the writable-erasable surface to be
substantially invisible.

[0048] Implementations and/or aspects may include one or more of the
following advantages. The coating surfaces are writable and erasable. The
coatings can provide writing surfaces that exhibit little or no image
ghosting, even after prolonged normal use. The coatings can be simple to
prepare, and can be applied to many different substrates, including both
porous (e.g., paper) and non-porous substrates (e.g., densified
ceramics). The coatings can be applied to various substrates including,
but not limited to, old chalkboards (e.g., blackboards), whiteboards,
drywalls, gypsum boards, plaster and painted walls. The water-based
coatings can be applied on the substrate on-site to make a
writable-erasable product rather than the writable-erasable product being
manufactured in a factory. For many substrates, a single coating can
provide an adequate writable-erasable surface. The coatings can exhibit
good adhesive strength to many substrates. Coating components (prior to
mixing) can have an extended shelf-life, e.g., up to about three years.
The coatings can be readily resurfaced. The coatings can cure rapidly,
e.g., in less than 4 hours, under ambient conditions. The coatings can
resist yellowing, as determined by ASTM method G-154, for an extended
period of time (e.g., up to 2000 hours). The coatings do not require UV
light or high-energy radiation, such as a beam of electrons, for curing.
Nevertheless, in some implementations, light, e.g., UV light, or heat can
be utilized to enhance the curing rate. The coatings can have a reduced
tendency to run, even when applied upon a vertical substrate. Surface
gloss of the coatings can be readily adjusted. The writing surface of the
coating can be projectable. The coatings can be hard. The coatings can be
substantially impervious to organic solvents and/or inks. The coatings
can have a low porosity. Surfaces of the coatings can have a low
roughness. The coatings can be impact resistant. The coatings can be made
scratch and abrasion resistant. The coatings can be relatively low cost.
The coatings can have a high chemical resistance.

[0049] "Curing" as used herein refers to one or more of solvent
evaporation (drying), radiation effected curing, coalescence, catalyzed
polymerization, oxidative cross-linking, or other methods of
cross-linking.

[0050] "Ambient conditions" as used herein refers to nominal, earth-bound
conditions as they exist at sea level at a temperature of about
45-130° F.

[0051] A "water-based carrier" as used herein is one that does not have
more than about 350 g/L of volatile organic compounds (VOCs), as
determined by the EPA Method 24.

[0052] "Substantially invisible" as used herein refers to a color
difference, Delta E (ΔE) of less than 10 as calculated according to
the ASTM Test Method D2244.

[0053] "Alkyl" as used herein refers to a saturated or unsaturated
hydrocarbon containing 1-20 carbon atoms including both acyclic and
cyclic structures (such as methyl, ethyl, propyl, isopropyl, butyl,
iso-butyl, sec-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl, propenyl, butenyl, cyclohexenyl and the like). A
linking divalent alkyl group is referred to as an "alkylene" (such as
ethylene, propylene and the like).

[0054] As used herein, "aryl" refers to monocyclic or polycyclic (e.g.,
having 2, 3 or 4 fused rings) aromatic hydrocarbons such as phenyl,
naphthyl, anthracenyl, phenanthrenyl, indanyl, indenyl, and the like. In
some embodiments, aryl groups have from 6 to about 20 carbon atoms, from
6 to about 15 carbon atoms, or from 6 to about 10 carbon atoms.

[0055] As used herein, "aralkyl" refers to alkyl substituted by aryl. An
example aralkyl group is benzyl.

[0056] As used herein, "alkoxy" refers to an --O-alkyl group. Example
alkoxy groups include methoxy, ethoxy, propoxy (e.g., n-propoxy and
isopropoxy), t-butoxy, and the like.

[0057] As used herein, "oxyalkylene" refers to an --O-alkylene group.

[0058] As used herein, "alkoxylate" refers to an alkyl-C(O)O. Example
alkoxylates include acetate, stearate and the like.

[0059] A "polyol" as used herein is a moiety that includes at least two
hydroxyl (--OH) groups. The hydroxyl groups can be terminal and/or
non-terminal. The hydroxyl groups can be primary hydroxyl groups.

[0060] A "polyurethane" as used herein is a polymeric or oligomeric
material that includes a urethane linkage, [NHC(═O)O], in its
backbone.

[0061] All publications, patent applications, patents, and other
references mentioned herein are incorporated by reference herein in their
entirety.

[0062] The details of one or more implementations of the disclosure are
set forth in the accompanying drawings, and in the description below.
Other features, and advantages will be apparent from the description and
drawings, and from the claims.

BRIEF DESCRIPTION OF DRAWINGS

[0063] FIG. 1 is a top view of a writable-erasable product.

[0064] FIG 1A is a cross-sectional view of the writable-erasable product
of FIG. 1, taken along 1A-1A.

[0065] FIG. 2 is a cross-sectional view of a droplet of water on a coating
and illustrates a method for determining contact angle.

[0067] FIG. 4 is a perspective view of a tablet of coated papers formed
from the roll of FIG. 3.

[0068] Like reference symbols in various drawings indicate like elements.

DETAILED DESCRIPTION

Writable-Erasable Product:

[0069] Referring to FIGS. 1 and 1A, a writable-erasable product 10
includes a substrate 12 and a cured coating 14 extending upon the
substrate 12. The coating 14 has a writable-erasable surface 16. When the
writable-erasable surface 16 is marked with a marking material, the
marking material can be erased from the writable-erasable surface to be
substantially invisible, resulting in little or no ghosting, even after
prolonged normal use, e.g., after about 5,000 cycles (e.g., about 10
cycles, about 50 cycles, about 100 cycles, about 500 cycles, about 1,000
cycles, about 2,000 cycles, about 3,000 cycles, about 4,000 cycles, about
5,000 cycles, about 6,000 cycles, about 7,000 cycles, about 8,000 cycles,
or about 9,000 cycles) of writing and erasing at the same position. The
visibility, or the lack thereof, of the erasing can be determined by
measuring the color change, Delta E (ΔE), on the writable-erasable
surface using a spectrophotometer (such as the SP-62 portable
spectrophotometer available from X-Rite), after marking on the surface
and erasing the marking. The marking material can include a colorant
(e.g., a pigment) and a solvent such as water, alcohol, acetate, alkoxy
alcohol, ketone, ketonic alcohol, ester, acetate, mineral spirit, or
mixtures thereof. The marking material can be selected from any of the
industry standard dry-erase markers.

[0070] The materials that form the coating 14 can be applied to many
different types of substrates, including porous (e.g., paper) and
non-porous substrates (e.g., densified ceramics). The substrate 12 could
be a flexible film or a rigid movable or immovable structure. Examples of
the substrate include, but are not limited to, a polymeric material (such
as polyester or polyamide), cellulosic material (such as paper), glass,
wood, wall (such as plaster or painted), fiber board (such as a
whiteboard in which the cured coating extends upon a fiber board),
particle board (such as a chalkboard or blackboard), gypsum board,
densified ceramics, stone (such as granite), and metal (such as aluminum
or stainless steel). The substrate could be a newly built structure or
even a old and worn out chalkboard, blackboard, or whiteboard. In some
instances, the surface of the substrate can be cleaned by sanding the
surface and priming the surface prior to application of the coating. In
some instances, the surface can also be cleaned with a cleaning agent
(e.g., a mild acid) in order to provide better adhesion of the coating to
the surface.

[0071] The materials that form the coating 14, prior to the application on
substrates, can have a pot life which is the time during which the
materials must be applied on the substrate. In some implementations, the
materials can have a pot life of from about 10 minutes to about 16 hours,
e.g., from about 30 minutes to about 12 hours, from about 60 minutes to
about 8 hours, from about 1 hour to about 4 hours, or from about 1 hour
to about 2 hours. In other implementations, the materials can have a pot
life of greater than about 6 months, e.g., about 12 months, about 18
months, about 24 months, about 30 months, or about 36 months.

[0072] The materials that form the coating 14, upon application to the
substrates, typically cure under ambient conditions. Curing, here, refers
to the process of setting of the materials that form the coating on the
substrate. It could refer to the process of simple evaporation of the
solvent from the materials that form the coating; the different methods
of crosslinking among the materials that form the coating including, but
not limited to, oxidative cross-linking and catalyzed polymerization.
Cross-linking between polymeric chains, either chemical or physical, can
influence certain unique properties of coatings. In some optional
implementations, the cure could be facilitated by UV-light, thermal
means, initiators, or electron-beam. The coating 14 can cure under
ambient conditions in from about 4 hours to about a week, e.g., from
about 4 hours to about 24 hours, from about 8 hours to about 20 hours,
from about 12 hours to about 16 hours, from about 1 day to about 7 days,
from about 2 days to about 6 days, or from about 3 days to about 5 days.

[0073] The materials that form the coating 14, emit little or no VOCs,
e.g., solvents and/or formaldehyde, during application to the substrate
12. The cured coatings 14 can be generally stable and can also emit
relatively little or no VOCs. The decreased amount of volatile content
(usually solvents) and ambient cure can reduce environmental impact and
can make the materials less toxic (decreased inhalation and absorption)
and safer (decreased flammability and flash point) to use. The reduced
emission of organic solvents during the application of the water-based
coating ensures that the application area need not be isolated from other
areas, need not be well ventilated, and that little or no personal
protection equipment is required. The use of ambient cure material allows
for energy efficiency during the curing process as compared to curing
processes that require energy in the form of radiation. The reduced
amounts of organic solvents can also lead to increased pot life of the
coating material and hence decreased material waste. Low VOC emissions
and ambient cure can also provide coatings and/or writable-erasable
surfaces that have one or more of the desirable attributes, such as low
porosity, low surface roughness, high elongation at break, high Taber
abrasion resistance, and high Sward hardness.

[0074] In some implementations, the material has less than about 350 g/L
of VOCs, e.g., about 300 g/L, about 250 g/L, about 200 g/L, about 150
g/L, about 100 g/L, about 50 g/L, or even less than about 0.5 g/L of
VOCs. In other implementations, the material has between about 0 and
about 50 g/L of VOCs, e.g., between about 1 g/L and about 10 g/L, between
about 10 g/L and about 20 g/L, between about 20 g/L and about 30 g/L,
between about 30 g/L and about 40 g/L, or between about 40 g/L and about
50 g/L of VOCs. The material may also be substantially free of VOCs.
Advantageously, when a VOC is utilized, it can be a VOC that is exempted
from United States Environmental Protection Agency (EPA) guidelines,
e.g., methyl acetate, t-butyl acetate, isopropyl alcohol, or acetone.

[0075] Porosity of the coatings can determine the amount of marking
material that can be trapped in the coating. Lower porosity percentages
of coatings can lead to better writable-erasable surfaces. In some
implementations, the coating 14 can have a porosity of between about 1
percent and about 40 percent, e.g., between about 2 percent and about 35
percent, between about 2.5 percent and about 30 percent, between about 3
percent and about 20 percent, or between about 4 percent and about 10
percent. In other implementations, the coating 14 can have a porosity of
less than about 40 percent, e.g., less than about 35 percent, less than
about 30 percent, less than about 25 percent, less than about 20 percent,
less than about 15 percent, less than about 10 percent, less than about 5
percent, or even less than about 2.5 percent. In some specific
implementations, the coating can have a porosity of about 3 percent,
about 33 percent or about 34 percent.

[0076] The coating 14 can be painted in a single coat or multiple coats
using a roller, spray painted, brush painted or using other types of
applicators. In some implementations, it can be painted using a foam
roller in a single coat. In some implementations, the coating 14 can have
a thickness, T (FIG. 1A), e.g., between about 0.001 inch and about 0.125
inch, e.g., between about 0.002 inch and about 0.1 inch, or between about
0.004 inch and about 0.08 inch, or between about 0.006 inch and about
0.06 inch, or between about 0.008 inch and about 0.04 inch, or between
about 0.01 inch and about 0.02 inch. In other implementations, the
coating 14 can have a thickness of greater than 0.005 inch, e.g., greater
than 0.0075 inch or greater than 0.010 inch. While not intending to be
bound by any theory, it is believed that providing an uniform, adequate
coating thickness, T, reduces the likelihood of thin or uncoated
substrate portions where marking material might penetrate.

[0077] In some implementations, the coating 14 can have a Taber abrasion
value of less than about 150 mg/thousand cycles, e.g., less than about
100 mg/thousand cycles, less than about 75 mg/thousand cycles, less than
about 50 mg/thousand cycles, less than about 35 mg/thousand cycles, less
than about 25 mg/thousand cycles, less than about 15 mg/thousand cycles,
less than about 10 mg/thousand cycles, less than about, less than about
2.5 mg/thousand cycles, less than about 1 mg/thousand cycles, or even
less than about 0.5 mg/thousand cycles. Maintaining a low Taber abrasion
value can provide long-lasting durability to the coating, reducing the
incidence of thin spots, which could allow penetration of marking
material through the coating and into the substrate.

[0078] In some implementations, the coating 14 can have a Sward hardness
of greater than about 10, e.g., greater than about 15, greater than about
25, greater than about 50, greater than about 75, greater than about 100,
greater than about 120, greater than about 150, or even greater than
about 200. While not intending to be bound by theory, it is believed that
maintaining a high Sward hardness provides long-lasting durability and
scratch resistance to the coating. Marking material entrapped in
scratches can be difficult to erase.

[0079] In some specific implementations, the coating can have a Sward
hardness of between about 10 and about 75, e.g., between about 15 and
about 70 or between about 15 and about 55. In some specific
implementations, the coating can have a Sward hardness of about 15, about
22 or about 25.

[0080] In some implementations, elongation at break for the coating
material can be between about 5 percent and about 400 percent, e.g.,
between about 25 percent and about 200 percent, or between about 50
percent and about 150 percent. In other implementations, the elongation
at break can be, e.g., greater than 10 percent, e.g., greater than 25
percent, greater than 50 percent, or even greater than 100 percent. While
not intending to be bound by theory, it is believed that maintaining high
elongation at break provides long-lasting durability to the coating, and
it allows the coating to be stressed without cracks forming. Cracks can
trap marking materials, making erasure from surfaces difficult and hence
decreasing the longevity of the writable-erasable products.

[0081] In some implementations, sag resistance for the coating material
can be about 8 mils, e.g., about 3 mils, about 4 mils, about 5 mils,
about 6 mils, about 7 mils, about 8 mils, about 9 mils, about 10 mils,
about 12 mils, about 14 mils, about 16 mils, about 18 mils, about 20
mils, about 22 mils, or about 24 mils. In other implementations, the
coating 14 can have sag resistance of from about 4 mils to about 24 mils,
e.g., from about 5 mils to about 20 mils, from about 6 mils to about 18
mils, from about 7 mils to about 16 mils, from about 8 mils to about 14
mils, from about 9 mils to about 12 mils, or from about 10 mils to about
12 mils.

[0082] In some implementations, the writable-erasable surface can have an
average surface roughness (Ra) of, e.g., between about 0.5 nm and
about 7,500 nm, e.g., between about 1 nm and about 6,000 nm, between
about 2 nm and about 5,000 nm, between about 5 nm and about 2,500 nm,
between about 10 nm and about 1,500 nm, between about 20 nm and about
1,000 nm or between about 25 nm and about 750 nm. In other
implementations, the coating 14 can have an average surface roughness
(Ra) of less than about 7,500 nm, e.g., less than about 5,000 nm,
less than about 3,000 nm, less than about 2,000 nm, less than about 1,000
nm, less than about 500 nm, less than about 250 nm, less than about 200
nm, less than about 100 nm, or even less than about 50 nm.

[0083] In some specific implementations, the writable-erasable surface can
have an average surface roughness (Ra) of between about 75 nm and
about 1,000 nm, e.g., between about 100 nm and about 500 nm or between
about 150 nm and about 400 nm. In some specific implementations, the
writable-erasable surface can have an average surface roughness (Ra)
of about 150 nm, about 300 nm or about 1,000 nm.

[0084] In some implementations, the writable-erasable surface can have a
maximum surface roughness (Rm) of less than about 10,000 nm, e.g.,
less than about 8,000 nm, less than about 6,500 nm, less than about 5,000
nm, less than about 3,500 nm, less than about 2,000 nm, less than about
1,000 nm, or less even than about 500 nm.

[0085] In some implementations, the writable-erasable surface can have a
flat finish (gloss below 15, measured at 85 degrees), an eggshell finish
(gloss between about 5 and about 20, measured at 60 degrees), a satin
finish (gloss between about 15 and about 35, measured at 60 degrees), a
semi-gloss finish (gloss between about 30 and about 65, measured at 60
degrees), or gloss finish (gloss greater than about 65, measured at 60
degrees).

[0086] In some specific implementations, the writable-erasable surface can
have a 60 degree gloss of between about 45 and about 90, e.g., between
about 50 and about 85. In other implementations, the writable-erasable
surface can have a 20 degree gloss of between about 10 and about 50,
e.g., between about 20 and about 45. In still other implementations, the
writable-erasable surface can have a 85 degree gloss of between about 45
and about 90, e.g., between about 75 and about 90. In other specific
implementations, the writable-erasable surface can have a 20 degree gloss
of about 12, about 23, or about 46; or a 60 degree gloss of about 52,
about 66, or about 85; or a 85 degree gloss of about 64, about 78, or
about 88.

[0087] In some implementations, to improve the writability and erasability
of the surface of the coating, precursor materials can be chosen so that
the cured coating has a surface that is relatively hydrophilic and not
very hydrophobic. Referring to FIG. 2, hydrophobicity of the
writable-erasable surface is related to its wetability by a liquid, e.g.,
water-based marking material. It is often desirable to quantitate the
hydrophobicity of the writable-erasable surface by a contact angle.
Generally, as described in ASTM D 5946-04, to measure contact angle,
θ, for a liquid (such as water) on the writable-erasable surface
16, an angle is measured between the writable-erasable surface 16 and a
tangent line 26 drawn to a droplet surface of the liquid at a three-phase
point. Mathematically, θ is 2arctan(A/r), where A is the height of
the droplet image, and r is half width at the base. In some
implementations, it can be desirable to have contact angle, θ,
measured using deionized water, of less than about 150 degrees, e.g.,
less than about 125 degrees, less than about 100 degrees, less than about
75 degrees or even less than about 50 degrees. In other implementations,
it can be desirable to have contact angle θ above about 35 degrees,
e.g., above about 40 degrees, above about 45 degrees.

[0088] In certain implementations, contact angle, θ, measured using
deionized water, can be between about 30 degrees and about 90 degrees,
e.g., between about 45 degrees and about 80 degrees, or between about 39
degrees and about 77 degrees. In some specific implementations, the
contact angle can be about 40 degrees, about 50 degrees, about 60
degrees, about 73 degrees, or about 77 degrees.

[0089] In some implementations, the writable-erasable surface can have a
surface tension of between about 30 dynes/cm and about 60 dynes/cm, e.g.,
between about 40 dynes/cm and about 60 dynes/cm. In some specific
implementations, the writable-erasable surface can have a surface tension
of about 25 dynes/cm, about 30 dynes/cm, about 42 dynes/cm, about 44
dynes/cm or about 56 dynes/cm.

[0090] In general, the coating 14 can be formed by applying, e.g.,
rolling, painting, or spraying, a solution of the material in a
water-based carrier that can have a sufficient viscosity such that the
applied coating does not run soon after it is applied or during its
curing. At the same time, the solution viscosity should be sufficient to
permit easy application. For example, in some implementations, the
applied solution can have a viscosity at 25° C. of between about
75 mPas and about 20,000 mPas, e.g., between about 200 mPas and about
15,000 mPas, between about 1,000 mPas and about 10,000 mPas, or between
about 750 mPas and about 5,000 mPas.

[0091] Advantageously, when the writable-erasable surface is marked with a
marking material that includes a colorant and a solvent that includes one
or more of water, alcohols, alkoxy alcohols, ketones, ketonic alcohols,
esters, acetates or mineral spirits, the marking material can be erased
from the writable-erasable surface to be substantially invisible.
Mixtures of any of the noted solvents may be used. For example, mixtures
of two, three, four or more of the noted, or other, solvents may be used.

[0092] In some implementations, the marking material can be erased from
the writable-erasable surface to be substantially invisible by wiping the
marks with an eraser that includes a fibrous material. For example, the
eraser can be in the form of a disposable wipe or a supported (e.g.,
wood, plastic) felt. The eraser can also include, e.g., one or more of
water, alcohols, alkoxy alcohols, ketones, ketonic alcohols, esters,
acetates or mineral spirits. Mixtures of any two or more of these
solvents may also be used.

[0093] Examples of alcohols include ethanol, n-propanol, iso-propanol,
n-butanol, iso-butanol, and benzyl alcohol. Mixtures of any two or more
of these solvents also represent alcohols.

[0094] Examples of alkoxy alcohols include 2-(n-propoxy)ethanol,
2-(n-butoxy)ethanol and 3-(n-propoxy)ethanol. Mixtures of any two or more
of these solvents also represent alkoxy alcohols.

[0095] Examples of ketones include acetone, methyl ethyl ketone and methyl
n-butyl ketone. Mixtures of any two or more of these solvents may also be
utilized.

[0096] Examples of acetates include methyl acetate, ethyl acetate, n-butyl
acetate and t-butyl acetate. Mixtures of any two or more of these
solvents may also be utilized.

[0097] For testing, the coating can be made by casting the material on a
fluoropolymer substrate, and then curing the material so that it can have
a dry thickness of about 0.002 inch. The cured sample can then be removed
from the fluoropolymer substrate to provide the test specimen. Testing
can be performed at 25° C. Elongation at break can be performed
using ASTM method D-882; porosity can be measured using mercury
porosimetry (suitable instruments available from Micromeritics, Norcross,
Ga., e.g., Micromeritics Autopore IV 9500); surface roughness can be
measured using atomic force microscopy (AFM) in tapping mode using ASME
B46.1 (suitable instruments, e.g., WYKO NT8000, are available from Park
Scientific); Taber abrasion resistance can be measured according to ASTM
method D-4060 (wheel CS-17, 1 kg load) and Sward hardness can be measured
according to ASTM method D-2134 (Sward Hardness Rocker Model C). The
amount of VOCs can be determined using the EPA Method 24. Gloss can be
measured using ASTM method D-523-89 (BYK Tri-Gloss Meter Cat. No. 4525).
Contact angle can be measured with deionized water using the dynamic
contact angle method (Angstroms Model FTA 200) using ASTM method
D-5946-04. Sag resistance can be measured using ASTM method D4400. This
is performed by obtaining a draw-down and measuring visually by
comparison with standard ASTM pictures. Surface tension can be measured
using AccuDyne Marking Pens. Stormer Viscosity can be measured on a
Brookfield Viscometer by ASTM method D-562 and reported in Kreb units
(Ku).

[0098] Any writable-erasable product described herein can have any one or
more of any of the attributes described herein. For example, the
writable-erasable surface can have an average surface roughness (Ra)
of less than about 7,500 nm, a maximum surface roughness (Rm) of
less than about 7,500 nm, a 60 degree gloss of less than about 50 and a
contact angle of less than about 100 degrees.

[0099] Any coatings described herein can have any one or more of any of
the following attributes. For example, the coating can have a porosity of
less than about 45 percent, an elongation at break of between about 25
percent and about 200 percent, and/or a Sward hardness of greater than
about 3 and a Taber abrasion value of less than about 150 mg/thousand
cycles.

Formulations

[0100] Water-based coatings, predominantly used in architectural settings,
contain binders, pigments, solvents, and/or additives. Some of the
polymer systems used in the water-based coatings realm are the acrylic
emulsions and urethane dispersions. Water-based coatings present
potential advantages in terms of reduced odor during curing and contain
lower VOCs compared to solvent-based coatings. It is also possible to
formulate water-based coatings containing none of the chemicals currently
classified as hazardous air pollutants (HAPs). The coating formulations,
in general, can include either a one-component system or a two-component
system. When the coating is formulated as a one-component system, the
coating can be formed from one or more materials, each of the one or more
materials including one or more functional groups independently selected
from G1, with at least one material of the one or more materials in a
water-based carrier. When the coating is formulated as a two-component
system, the coating can be formed from two or more materials. The first
material can include one or more functional groups independently selected
from G1 and the second material can include one or more functional groups
independently selected from G2, with at least one material of the one or
more materials in a water-based carrier. Each G1 functional group in
either the one-component or two-component system is independently
selected from among isocyanate, epoxide, urethane, ethyleneoxy, and
ethylene, wherein the ethylene is optionally substituted with hydroxyl,
acetoxy, or alkoxycarbonyl. Each G2 functional group in the two-component
system is independently selected from among hydroxyl, amine, phenol,
carboxylic acid, acid anhydride, aziridine, and thiol. Although water is
the predominant carrier, water-based coatings can contain less than about
15% of non-aqueous solvents to abet in film forming capabilities.

Polyurethanes

[0101] Polyurethanes can be obtained by the reaction of a diisocyanate or
polyisocyanate with a diol, or a polyol. Polyurethanes exhibit a wide
range of hardness and flexibility depending on various components
including the nature of the isocyanate and/or the polyol in addition to
the nature of curing. Polyurethane coatings could either be formulated as
one component or two component coatings. Reactive polyurethane coatings
involve the isocyanate as the reactive group during curing. See: The ICI
Polyurethanes Book, George Woods. (John Wiley & Sons: New York, 1987),
and Organic Coatings-Properties, Selection and Use U.S. Department of
Commerce, National Bureau of Standards: Washington D.C., Series 7;
February 1968, the complete disclosures of which are incorporated by
reference herein. Polyurethane coatings have also been categorically
assigned several ASTM designations (Types I-VI).

[0102] The coating 14 can be formed from one or more materials including
diisocyanate (G1=isocyanate) and one or more materials including hydroxyl
(G2=hydroxyl), at least one of these materials being in a water-based
carrier. In some implementations, the coating can be or includes a
reaction product of a first component that includes an isocyanate and a
second component that includes a polyol. Diisocyanates for use in
polyurethane applications, in general, can be obtained by the reaction of
amines with phosgene. Examples of organic diisocyanates include
aliphatic, cycloaliphatic (alicyclic), and aromatic diisocyanates. e.g.,
methylene diisocyanate, tetramethylene diisocyanate, hexamethylene
diisocyanate (HDI), octamethylene diisocyanate, decamethylene
diisocyanate, 2-methylpentane-1,5-diisocyanate, toluene diisocyanate
(TDI), diphenylmethane diisocyanate (MDI), m- and p-phenylene
diisocyanates, 4-chloro-m-phenylene diisocyanate, bitolylene
diisocyanate, cyclohexane diisocyanate (CHDI), bis-(isocyanatomethyl)
cyclohexane (H6XDI), dicyclohexylmethane diisocyanate (H12MDI), dimer
acid diisocyanate (DDI), trimethyl hexamethylene diisocyanate, lysine
diisocyanate and its methyl ester, methyl cyclohexane diisocyanate,
1,5-napthalene diisocyanate, xylene diisocyanate, polyphenylene
diisocyanates, isophorone diisocyanate (IPDI), hydrogenated methylene
diphenyl isocyanate (HMDI), tetramethyl xylene diisocyanate (TMXDI),
4-t-butyl-m-phenylenediisocyanate, 4,4'-methylene bis(phenyl isocyanate),
tolylene diisocyanate, 4-methoxy-m-phenylene diisocyanate, biphenylene
diisocyanate, cumene-2,4-diisocyanate, 3,3'-dimethyl-4,4'-biphenylene
diisocyanate, p,p'-diphenylene diisocyanate, or oligomers and
homopolymers thereof, and mixtures thereof In some embodiments, the
aliphatic diisocyanate, their oligomeric prepolymers, or aliphatic
polyisocyanate can be hydrophilic.

[0103] The monomeric diisocyanates may further be converted into
oligomeric prepolymers of higher molecular weight by treatment with diols
or triols. Such oligomeric prepolymers can also be used as a reaction
component in the production of the polyurethane coating. Diisocyanates
for use in polyurethane applications can be available from various
commercial vendors under different trade names. Examples of commercial
diisocyanates include, but are not limited to, diphenylmethane
diisocyanate (MDI) containing Isonate® Papi®, Spectrim®
(available from Dow chemical company), Desmodur® polyisocyanates and
Bayhydur® (available from Bayer), Sovermol® (available from
Cognis), Reafree®, and Chempol® (both available from Cook
Composite Polymers)

[0104] In some implementations, the percentage weight of homopolymer of
aliphatic diisocyanate in the total material formulation can be about
31%, e.g., about 26%, about 27%, about 28%, about 29%, about 30%, about
31%, about 32%, about 33%, about 34%, or even about 35%. In some
implementations, the percentage weight of homopolymer of aliphatic
diisocyanate in the total material formulation can be from about 20% to
about 40%, e.g., from about 22% to about 38%, from about 24% to about
36%, from about 26% to about 34%, or from about 28% to about 32%.

[0105] The isocyanate containing material of the formulation can have a
viscosity of about 91 Kreb Units (Ku), e.g., about 85 Ku, about 90 Ku,
about 95 Ku, about 100 Ku, or about 105 Ku. In some implementations, the
isocyanate containing material of the formulation can have a viscosity of
from about 40 Ku to about 140 Ku, e.g., from about 60 Ku to about 105 Ku,
from about 70 Ku to about 105 Ku, or from about 80 Ku to about 95 Ku.

[0106] The polyurethane coatings can also contain polyurethane resins
(G1=urethane). In some implementations, the polyurethane resins can be in
the form of dispersions of urethane prepolymers and oligomers in a
water-based carrier. In some implementations, the polyurethane
dispersions can be formulated as either one component or two component
coatings.

Epoxies

[0107] An epoxy coating formulation can be obtained by mixing an epoxy
resin with a curing agent. The epoxy resins are polyether chains that
contain one or more epoxide units in their structure. Polyethers have the
repeating oxyalkylene units: alkylene substituted by oxygen groups, e.g.,
ethyleneoxy, --[CH2--CH2O]--. In some implementations, the
polyether chains can have additional functional groups such as hydroxyl
(--OH). Curing of epoxy resins can lead to less amount of volatile
products. Due to the unique properties of the epoxide ring structure, the
curing agents can be either nucleophilic or electrophilic. Nucleophilic
agents such as alcohols, phenols, amines, amino silanes, thiols,
carboxylic acids, and acid anhydrides can be used. In some
implementations, these curing agents can contain one or more nucleophilic
groups. The epoxy resins themselves can contain an aliphatic (such as,
cyclic or acyclic), aromatic backbone or a combination of both. In some
optional implementations, the epoxy resins can contain other
non-interfering chemical linkages (such as alkyl chains).

[0108] The coating 14 can be formed from a epoxy material (G1=epoxide) and
a hydroxyl or an amine material, at least one of these materials being in
a water-based carrier. In some implementations, the material can be or
includes a reaction product of a first component that includes an epoxide
or oxirane material (such as an epoxy prepolymer) in a water-based
carrier and a second component that includes an alcohol, an alkyl amine
(such as, cyclic or acyclic), a polyol, a polyamine (such as
isophoronediamine), a polyester polyamine, or an amido polyamine in a
water-based carrier. In such implementations, the epoxide or oxirane
material can serve as a crosslinking material. In some specific
implementations, the epoxide material can be epichlorohydrin, glycidyl
ether type (such as diglycidyl ether of bisphenol-A), oxirane modified
fatty acid ester type, or oxirane modified ester type. In some specific
implementations, the polyol material can be a polyester polyol, polyamine
polyol, polyamide polyol, or amine adduct polyol. In some
implementations, the epoxy coating can be formulated as either one
component or two component coatings.

Acrylics

[0109] Polyacrylates have the repeating units of ethylene substituted by
alkoxycarbonyl groups: --[CH2--CH(X)]--, where X is alkylOC(O)--.
Acrylic emulsions have found applications in water-borne coatings. The
acrylic emulsions can include dispersions of acrylic monomers with a
cross-linking catalyst; acrylic copolymers which are capable of
self-crosslinking; styrene acrylic copolymers; or functionalized acrylic
copolymers.

[0110] In some optional implementations, the material can be or includes
an acrylic material in a water-based carrier. In such implementations,
the acrylic material can be methyl methacrylate based, butyl acrylate
based, ethyl acrylate based, or their mixtures. In such implementations,
an polycarbodiimide, an aziridine, or an imidazoline material can serve
as an external crosslinking material. In such implementations, the
acrylic coating can be formulated as a one or a two component system.

Vinylic Polymers

[0111] Aqueous dispersions of the acrylic vinylic copolymers form the core
material of this type of formulations. The copolymerization of the
polyvinyl acetate with ethylene provides varying flexibility and
transparency required in many coatings. Polyvinyl acetate has the
repeating units of ethylene substituted by acetoxy groups:
--[CH2--CH(X)]--, where X is CH3C(O)O--, an acetate.
Polyethylene has the repeating units of ethylene:
--[CH2--CH2]--. In some implementations, the material can be or
includes an vinyl resin material in a water-based carrier. In such
implementations, the vinylic material can be polyvinyl acetate, polyvinyl
acetate-ethylene copolymer, polyvinyl alcohol (--[CH2--CH(X)]--,
where X is OH) or a thio functionalized vinylic copolymer. In such
implementations, the material can be a one component system.

Hybrid Systems

[0112] Some or all of the formulation systems mentioned above may be
combined together to form a hybrid system. The hybrid systems can either
be a hybrid copolymer system in a homogeneous medium or a hybrid
dispersion. Hybrid dispersions contain two chemical classes which
interact cooperatively to provide desired properties, typically in a
water-based carrier. In some implementations, the material can be a one
or a two component hybrid material in a water-based carrier. In such
implementations, the hybrid material can be a combination of
polyurethane/acrylic, epoxy/acrylic, alkyd/acrylic, or polyvinyl
alcohols. In such implementations, an external crosslinker can include an
polycarbodiimide, an aziridine, or an imidazoline.

[0113] In some implementations, the material can be a one component hybrid
material in a water-based carrier. In such implementations, the hybrid
material can be a combination of polyurethane dispersion (PUD)/acrylic,
polyvinyl acetate/acrylic, polyvinyl acetate/epoxy, polyvinyl
acetate/polyurethane, or polyvinyl alcohols. In such implementations, an
external crosslinker can include an polycarbodiimide, an aziridine, or an
imidazoline.

Polyols

[0114] An acrylic polyol is an example of a polyol that can be reacted
with the reactive groups such as isocyanates, epoxides and other such
reactive groups to produce the coatings. Acrylic polyols can be typically
obtained by polymerization (free-radical mediated) of hydroxyacrylates
and styrene. Examples of hydroxyacrylates include butanediol monoacrylate
(BDMA), 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl acrylate (HPA),
hydroxybutyl acrylate, polycaprolactone modified hydroxyethyl
hexylacrylate. In some implementations, the percentage weight of acrylic
polyol in the total material formulation can be about 16%, e.g., about
12%, about 13%, about 14%, about 15%, about 17%, or even about 18%. In
some implementations, the percentage weight of acrylic polyol in the
total material formulation can be from about 10% to about 20%, e.g., from
about 11% to about 19%, from about 12% to about 18%, from about 13% to
about 17%, or from about 14% to about 16%.

[0115] A polyoxyalkylene diol is an example of another polyol that can be
used to produce the coatings. In some implementations, the
polyoxyalkylene diols have a number average molecular weight of from
about 200 to 3,000, e.g., from about 500 to about 2,000, as determined
using narrow disperse polyethylene glycol standards. Specific examples of
polyoxyalkylene diols include polyethyleneether glycol,
polypropyleneether glycol, polybutyleneether glycol,
polytetramethyleneether glycol, and copolymers of polypropyleneether and
polyethyleneether glycols. Mixtures of any of the polyoxyalkylene diols
can also be used.

[0116] Polyester polyols or polyester diols are polyesters having terminal
hydroxyl groups and are examples of polyols that can be used to produce
the coatings. Such polyester diols can be prepared by the condensation of
a diol, such as ethylene glycol, propanediol-1,2, propanediol-1,3,
butanediol-1,3, butanediol-1,4, pentanediol-1,2, pentanediol-1,5,
hexanediol-1,3, hexanediol-1,6, diethylene glycol, dipropylene glycol,
triethylene glycol, tetraethylene glycol, or mixtures of these diols,
with a dicarboxylic acid or an equivalent thereof, e.g., acid halide or
anhydride. Examples of acids include oxalic, malonic, succinic, glutaric,
adipic, pimelic, suberic, azelaic, terephthalic, sebacic, malic,
phthalic, cylohexanedicarboxylic or mixtures of these acids. When
preparing these polyester diols, generally an excess of the diol over
dicarboxylic acid is used.

[0117] Polyamide diols or polyamide polyols having terminal hydroxyl
groups are yet another example of a polyol that can be used to produce
the coatings.

[0118] Polyamine polyols having terminal hydroxyl groups are yet another
example of a polyol that can be used to produce the coatings.

[0119] Polyepoxy polyol having terminal hydroxyl groups are yet another
example of a polyol that can be used to produce the coatings.

[0120] Polyvinyl polyol having terminal hydroxyl groups are yet another
example of a polyol that can be used to produce the coatings.

[0121] A polyurethane diol, having terminal hydroxyl groups is yet another
example of a polyol that can be used to produce the coatings. The
polyurethane diols can include polyalkylene, poly(oxyalkylene),
polyester, polyamide, polycarbonate, polysulfide, polyacrylate,
polymethacrylate, or mixtures of any of these functionalities along its
backbone. In some implementations, the polyurethane diols have a number
average molecular weight of from about 200 to 3,000, e.g., from about 500
to about 2,000, as determined using narrow disperse polyethylene glycol
standards. Polyurethane diols can be advantageously utilized to provide
particularly wear and scratch resistant coatings. The polyurethane having
terminal hydroxyl groups can be prepared by a reaction of any one or more
of the polyols discussed above and an organic diisocyanate to provide a
isocyanate terminated prepolymer, followed by reaction of the prepolymer
with a polyhydric alcohol containing 2-6 hydroxyl groups. Some
polyurethane diols are commercially available from Sigma-Aldrich
chemicals or King industries.

[0122] The diol can be reacted with the diisocyanate utilizing a molar
ratio of about 1:2, respectively, in the presence of an activator (or
accelerator) such as oxazolidine or an organotin compound, e.g.,
dibutyltin dilaurate or dibutyltin dioctoate. The reaction can be allowed
to proceed at a temperature of from about 60° C. to about
180° C., from about 4 hours to about 24 hours to provide the
isocyanate terminated prepolymer.

[0123] The isocyanate terminated urethane prepolymer can then be reacted,
e.g., at from about 60° C. to about 110° C. for 1 to about
10 hours, with a monomeric, polyhydric alcohol containing 2-6 hydroxyl
groups in a molar ratio of 1:2, respectively. Examples of alcohols that
can be used include 1,4-cyclohexane dimethanol, 1,4-butanediol, mannitol,
trimethylol propane, trimethylol ethane, 1,1-cyclohexane dimethanol,
hydrogenated bisphenol A, cyclohexane diol, neopentyl glycol,
trimethylpentanediol, pentaerythritol, and trimethylhexanediol. The
result of treating the isocyanate terminated urethane prepolymer with the
one or more alcohols is a polyurethane diol having 2-10 terminal hydroxyl
groups and no isocyanates groups.

[0124] Polyurethane diols can also be made by reacting organic carbonates
with amines.

[0125] In some implementations in which a polyurethane diol is used to
make the coating, the molar proportion of polyurethane diol to the
alkoxyalkylamino material can range from about 10:1 to about 1:1, e.g.,
5:1 to 1:1.

[0126] Examples of commercial polyols include, but are not limited to,
Desmophen® (available from Bayer), Macrynal® (available from
Cytec Industries), and Arolon® (available from Reichold).

[0127] In some implementations, the material can include an external
crosslinker, such as a polycarbodiimide, an aziridine, or an imidazoline.

Other Implementations:

[0128] In some optional implementations, the material can be or includes a
reaction product of a first component that includes an alkoxyalkylamino
material in a water-based carrier and a second component that includes a
polyol in a water-based carrier. In such implementations, the
alkoxyalkylamino material can serve as a crosslinking material.

[0129] In yet other optional implementations, the material can be or
includes an alkyd material in a water-based carrier. In such
implementations, the oil part of the material can be castor oil, soybean
oil, sunflower oil, soya oil, linseed oil, or their mixtures. In such
implementations, the material can be a one or a two component system.

[0130] In yet other optional implementations, the material can be selected
from fluorine based resins or silica based resins. In such
implementations, the material can be a one or a two component system.

[0131] In yet other optional implementations, the material can be selected
from a rosin phenolic, an epoxy ester, polyurea, polyaspartics, or adipic
dihydrazine based. In such implementations, the material can be a two
component system.

Solvents

[0132] The coating 14 can be formed from a material in a water-based
carrier. While not intending to be bound by theory, it is believed that
solvents can be effective as a dispersive vehicle for the pigments and
resins in a coating formulation prior to curing. During the application
of the formulation, they aid in achieving an appropriate viscosity of the
formulation. However, after the coating has been cured, it can be
expected that there is no residual solvent. The solvents can include
2-butoxyethanol, ethylene glycol, ethyl benzene, xylenes, methyl amyl
ketone, isopropyl alcohol, propylene glycol monomethyl ether, ethylene
glycol monobutyl ether, butanol, paraffins, alkanes, polypropylene
glycol, Stoddard solvent, toluene, ethoxylated alkylphenol,
1-methyl-2-pyrrolidinone, or 1-ethylpyrrolidin-2-one.

[0137] Examples of defoaming agents include polyethylene glycols, or
silicone surfactants, e.g., polyether modified polydimethyl siloxane.
Defoaming agents such as BYK family of agents are available from
BYK-Chemie GmbH.

[0138] Examples of viscosity modifying agents include polyurethanes, or
Tafigel®, a commercial acrylic copolymer available from Munzing
Chemie GmbH.

[0139] Certain implementations are further described in the following
examples, which are not intended to limit the scope of the disclosure.

EXAMPLES

Example 1

[0140] First Component: During the grind stage, to the pot were added, in
order, in the ranges of weight % listed in Table 1: oxirane-modified
fatty acid ester, Stoddard solvent, butyl glycolate, 2-butoxyethanol,
alkylaryl alkoxylate, ester/styrene maleic anhydride copolymer, ethylene
glycol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, ethyl benzene and xylene
(mixed isomers). The contents were then mixed at slow speeds until fully
dispersed. The speed was maintained at no more than 100-200 rpm. Titanium
dioxide, aluminum hydroxide, amorphous silica and water were then added
to the mixture in the pot, while increasing the speed to achieve a good
vortex. Final RPM settings were between 2,000-3,000 rpm. The speed was
adjusted until maximum shear was obtained with minimal integration of air
and mixed for 10-15 minutes, or a Hegman of 5-6. After ascertaining that
there were no chunks, the speed was increased to achieve sufficient
vortex. A sufficient RPM was maintained while keeping the temperature in
the pot below 95-110° F. Hegman at this point was at least a 7.
Once Hegman was achieved, mixing speed was reduced until the pot was just
mixing the raw materials and continued for 10-15 minutes.

[0141] During the letdown stage, propylene glycol monomethyl ether, methyl
amyl ketone and isopropyl alcohol were added to the grind mixture. The
speed was maintained to mix the material. After 15-20 minutes the product
was packaged.

[0142] Second Component: The high acid value polyester, ethylene glycol
monobutyl ether and isopropyl alcohol mixture was the second component of
the final product. No mixing was required for these materials.

[0143] Combining the First and Second Components: The first and second
components were combined, when desired, to obtain the final coating
formulation. The combination had a pot life of a maximum of about 1 hour
during which time the application was completed. The composition of the
formulation is described in Table 1.

[0144] First Component: During the grind stage, to the pot were added, in
order, in the ranges of weight % listed in Table 2: water,
polyetherpolysiloxane, polyalkylene oxide, alkylarylalkoxylate,
ester/styrene maleic anhydride copolymer, ethylene glycol,
2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2-butoxyethanol, polypropylene
glycol and polysiloxanes. The contents were then mixed at slow speeds
until fully dispersed. The speed was maintained at no more than 100-200
rpm. Titanium dioxide, aluminum hydroxide, amorphous silica and water
were added to the mixture in the pot, while increasing the speed to
achieve a good vortex. Final RPM settings were between 2,000-3,000 rpm.
The speed was adjusted until maximum shear was obtained with minimal
integration of air and mixed for 10-15 minutes, or a Hegman of 5-6. After
ascertaining that there were no chunks, the speed was increased to
achieve sufficient vortex. A sufficient RPM was maintained while keeping
the temperature in the pot below 95-110° F. Hegman at this point
was at least a 7. Once Hegman was achieved, mixing speed was reduced
until the pot was just mixing the raw materials and continued for 10-15
minutes.

[0145] During the letdown stage, methyl benzimidazole-2-yl carbamate,
Koalin, 3-iodo-2-propynyl butyl carbamate, synthetic fatty acids modified
acrylic copolymer and butanol, were added to the grind mixture. The speed
was maintained to mix the material. After 15-20 minutes the product was
packaged.

[0146] Second Component: The mixture of N,N-dimethylcyclohexylamine,
hexamethylene-1,6-diisocyanate and hydrophilic aliphatic polyisocyanate
based on hexamethylene diisocyanate was the second component of the final
product. No mixing was required for these materials.

[0147] Combining the First and Second Components: The first and second
components were combined, when desired, to obtain the final coating
formulation. The combination had a pot life of a maximum of about 1 hour
during which time the application was completed. The composition of the
formulation is described in Table 2.

[0148] First Component: During the grind stage, to the pot were added, in
order, in the ranges of weight % listed in Table 3: water,
polyetherpolysiloxane, polyalkylene oxide, alkylarylalkoxylate,
ester/styrene maleic anhydride copolymer, ethylene glycol,
2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2-butoxyethanol, polypropylene
glycol and polysiloxanes. The contents were then mixed at slow speeds
until fully dispersed. The speed was maintained at no more than 100-200
rpm. Titanium dioxide, aluminum hydroxide, amorphous silica and water
were added to the mixture in the pot, while increasing the speed to
achieve a good vortex. Final RPM settings were between 2,000-3,000 rpm.
The speed was adjusted until maximum shear was obtained with minimal
integration of air and mixed for 10-15 minutes, or a Hegman of 5-6. After
ascertaining that there were no chunks, the speed was increased to
achieve sufficient vortex. A sufficient RPM was maintained while keeping
the temperature in the pot below 95-110° F. Hegman at this point
was at least a 7. Once Hegman was achieved, mixing speed was reduced
until the pot was just mixing the raw materials and continued for 10-15
minutes.

[0149] During the letdown stage, 2-amino-2-methyl-1-propanol,
2-(methylamino)-2-methyl-1-propanol, methyl benzimidazole-2-yl carbamate,
Koalin and 3-iodo-2-propynyl butyl carbamate were added to the grind
mixture. After less than 5-10 minutes, synthetic fatty acids modified
acrylic copolymer and butanol were added to the pot. The speed was
maintained to mix the material. After 15-20 minutes the product was
packaged.

[0150] Second Component: The mixture of homopolymer of
hexane-1,6-diisocyanate, n-butyl acetate, polyoxyethylene tridecyl ether
phosphate, N,N-dimethyl-cyclohexanamine, 1,6-diisocyanato-hexane and
isophorone diisocyanate was the second component of the final product. No
mixing was required for these materials.

[0151] Combining the First and Second Components: The first and second
components were combined, when desired, to obtain the final coating
formulation. The combination had a pot life of a maximum of about 1 hour
during which time the application was completed. The composition of the
formulation is described in Table 3.

[0152] First Component: During the grind stage, to the pot were added, in
order, in the ranges of weight % listed in Table 4: water, poly amine
adduct, tetraethylenepentamine, a mixture of polymers and hydrophobic
polymers, 2-ethyl-1hexanol, paraffins, and modified polyacrylate. The
contents were then mixed at slow speeds until fully dispersed. The speed
was maintained at no more than 100-200 rpm. Titanium dioxide, aluminum
hydroxide, amorphous silica and water were added to the mixture in the
pot, while increasing the speed to achieve a good vortex. Final RPM
settings were between 2,000-3,000 rpm. The speed was adjusted until
maximum shear was obtained with minimal integration of air and mixed for
10-15 minutes, or a Hegman of 5-6. After ascertaining that there were no
chunks, the speed was increased to achieve sufficient vortex. A
sufficient RPM was maintained while keeping the temperature in the pot
below 95-110° F. Hegman at this point was at least a 7. Once
Hegman was achieved, mixing speed was reduced until the pot was just
mixing the raw materials and continued for 10-15 minutes.

[0153] During the letdown stage, alkanes, 2-butoxyethanol and ethoxylated
alkylphenol were added to the grind mixture. The speed was maintained to
mix the material. After less than 5-10 minutes, acrylic nonionic
copolymer and 2-methoxymethylethoxy-propanol were added to the pot. The
speed was maintained to mix the material. After less than 5-10 minutes,
solution of modified urea, 1-methyl-2-pyrrolidone and lithium chloride
were added to the pot. The speed was maintained to mix the material.
After less than 5-10 minutes, polysiloxane and polyethylene glycol were
added to the pot. The speed was maintained to mix the material. After
15-20 minutes the product was packaged.

[0154] Second Component: The diglycidyl ether of bisphenol-A homopolymer
mixture was the second component of the final product. No mixing was
required for these materials.

[0155] Combining the First and Second Components: The first and second
components were combined, when desired, to obtain the final coating
formulation. The combination had a pot life of a maximum of about 1-2
hours during which time the application was completed. The composition of
the formulation is described in Table 4.

[0156] First Component: During the grind stage, to the pot were added, in
order, in the ranges of weight % listed in Table 5: water, xylene,
polypropylene glycol, polysiloxanes, functionalized polyacrylate
copolymer, alkanes, 2-butoxyethanol and ethoxylated alkylphenol. The
contents were then mixed at slow speeds until fully dispersed. The speed
was maintained at no more than 100-200 rpm. Titanium dioxide, aluminum
hydroxide, amorphous silica and water were added to the mixture in the
pot, while increasing the speed to achieve a good vortex. Final RPM
settings were between 2,000-3,000 rpm. The speed was adjusted until
maximum shear was obtained with minimal integration of air and mixed for
10-15 minutes, or a Hegman of 5-6. After ascertaining that there were no
chunks, the speed was increased to achieve sufficient vortex. A
sufficient RPM was maintained while keeping the temperature in the pot
below 95-110° F. Hegman at this point was at least a 7. Once
Hegman was achieved, mixing speed was reduced until the pot was just
mixing the raw materials and continued for 10-15 minutes.

[0157] During the letdown stage, 2-amino-2-methyl-1-propanol and
2-(methylamino)-2-methyl-1-propanol were added to the grind mixture.
After less than 5-10 minutes, N,N-diethylethanamine, polyurethane resin
and 1-methyl-2-pyrrolidinone were added to the pot. The speed was
maintained to mix the material. After less than 5-10 minutes,
fluoroaliphatic polymeric esters +(5049P), residual organic
fluorochemicals, toulene and fluorochemical monomers were added to the
pot. The speed was maintained to mix the material. After less than 5-10
minutes polyurethane resin was added to the pot. After less than 5-10
minutes, polyurethane resin was added to the pot. The speed was
maintained to mix the material. After 15-20 minutes the product packaged.

[0158] Second Component: The polyfunctional aziridine mixture was the
second component of the final product. No mixing was required for these
materials.

[0159] Combining the First and Second Components: The first and second
components were combined, when desired, to obtain the final coating
formulation. The combination had a pot life of a maximum of about 1 hour
during which time the application was completed. The composition of the
formulation is described in Table 5.

[0160] During the grind stage, to the pot were added, in order, in the
ranges of weight % listed in Table 6: water, propylene glycol, xylene,
polypropylene glycol, polysiloxanes, polycarboxylate-sodium salt,
alkanes, 2-butoxyethanol and ethoxylated alkylphenol. The contents were
then mixed at slow speeds until fully dispersed. The speed was maintained
at no more than 100-200 rpm. Titanium dioxide, aluminum hydroxide,
amorphous silica and water were added to the mixture in the pot, while
increasing the speed to achieve a good vortex. Final RPM settings were
between 2,000-3,000 rpm. The speed was adjusted until maximum shear was
obtained with minimal integration of air and mixed for 10-15 minutes, or
a Hegman of 5-6. After ascertaining that there were no chunks, the speed
was increased to achieve sufficient vortex. A sufficient RPM was
maintained while keeping the temperature in the pot below 95-110°
F. Hegman at this point was at least a 7. Once Hegman was achieved,
mixing speed was reduced until the pot was just mixing the raw materials
and continued for 10-15 minutes.

[0161] During the letdown stage, vinyl acetate/ethylene copolymer was
added to the grind mixture. After less than 5-10 minutes,
2,2,4-trimethyl-1,3-pentanediol monoisobutyrate was added to the pot. The
speed was maintained to mix the material. After less than 5-10 minutes,
polyurethane resins and enzymatically modified starch were added to the
pot. The speed was maintained to mix the material. After 15-20 minutes
the product was packaged. The composition of the formulation is described
in Table 6.

[0162] During the grind stage, to the pot were added, in order, in the
ranges of weight % listed in Table 7: water, N,N-diethylethanamine,
polyurethane resin, 1-methyl-2-pyrrolidinone, alkanes, 2-butoxyethanol
and ethoxylated alkylphenol. The contents were then mixed at slow speeds
until fully dispersed. The speed was maintained at no more than 200-400
rpm. There was no Hegman grind to measure in this formula. Once blending
was achieved, mixing speed was reduced until the pot was just mixing the
raw materials and continued for 10-15 minutes. The speed was maintained
to mix the material. After 15-20 minutes the product was packaged. The
composition of the formulation is described in Table 7.

[0163] During the grind stage, to the pot were added, in order, in the
ranges of weight % listed in Table 8: water,
chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one,
magnesium chloride, magnesium nitrate, polycarboxylate-sodium salt,
ammonium hydroxide,
α-(phenylmethyl)-ω-(1,1,3,3,-tetramethylbutyl)phenoxy
poly(oxy-1-2-ethanediyl), mono{(1,1,3,3-tetramethylbutyl)phenyl}ether
polyethylene glycols, xylene and polysiloxanes. The contents were then
mixed at slow speeds until fully dispersed. The speed was maintained at
no more than 100-200 rpm. Titanium dioxide, aluminum hydroxide, amorphous
silica and water were added to the mixture in the pot, while increasing
the speed to achieve a good vortex. Final RPM settings were between
2,000-3,000 rpm. The speed was adjusted until a maximum shear was
obtained with minimal integration of air and mixed for 10-15 minutes, or
a Hegman of 5-6. After ascertaining that there were no chunks, the speed
was increased to achieve sufficient vortex. A sufficient RPM was
maintained while keeping the temperature in the pot below 95-110°
F. Hegman at this point was at least a 7. Once Hegman was achieved,
mixing speed was reduced until the pot was just mixing the raw materials
and continued for 10-15 minutes.

[0164] During the letdown stage, acrylic monomers were added to the grind
mixture. After less than 5-10 minutes, 2,2,4-trimethyl-1,3-pentanediol
monoisobutyrate was added to the pot. The speed was maintained to mix the
material. After less than 5-10 minutes, polyurethane resin and
2-butoxyethanol were added to the pot. The speed was maintained to mix
the material. After less than 5-10 minutes polyethylene glycol
octylphenyl ether and poly(ethylene oxide) were added to the pot. The
speed was maintained to mix the material. After less than 5-10 minutes,
propylene glycol was added to the pot. The speed was maintained to mix
the material. After less than 5-10 minutes, polyurethane resin was added
to the pot. The speed was maintained to mix the material. After 15-20
minutes the product was packaged. The composition of the formulation is
described in Table 8.

[0165] During the grind stage, to the pot were added, in order, in the
ranges of weight % listed in Table 9: water, xylene, polypropylene
glycol, polysiloxanes, functionalized polyacrylate copolymer, alkanes,
2-butoxyethanol and ethoxylated alkylphenol. The contents were then mixed
at slow speeds until fully dispersed. The speed was maintained at no more
than 100-200 rpm. Titanium dioxide, aluminum hydroxide, amorphous silica
and water were added to the mixture in the pot, while increasing the
speed to achieve a good vortex. Final RPM settings were between
2,000-3,000 rpm. The speed was adjusted until maximum shear was obtained
with minimal integration of air and mixed for 10-15 minutes, or a Hegman
of 5-6. After ascertaining that there were no chunks, the speed was
increased to achieve sufficient vortex. A sufficient RPM was maintained
while keeping the temperature in the pot below 95-110° F. Hegman
at this point was at least a 7. Once Hegman was achieved, mixing speed
was reduced until the pot was just mixing the raw materials and continued
for 10-15 minutes.

[0166] During the letdown stage, 2-amino-2-methyl-1-propanol and
2-(methylamino)-2-methyl-1-propanol were added to the grind mixture.
After less than 5-10 minutes, N,N-diethylethanamine, polyurethane resin
and 1-methyl-2-pyrrolidinone were added to the pot. The speed was
maintained to mix the material. After less than 5-10 minutes,
fluoroaliphatic polymeric esters +(5049P), residual organic
fluorochemicals, toluene and fluorochemical monomer were added to the
pot. The speed was maintained to mix the material. After less than 5-10
minutes polyurethane resin was added to the pot. The speed was maintained
to mix the material. After less than 5-10 minutes, polyurethane resin was
added to the pot. The speed was maintained to mix the material. After
15-20 minutes the product packaged. Pot life on the mixture was greater
than 4 hours but less than 24 hours. The composition of the formulation
is described in Table 9.

[0167] During the grind stage, to the pot were added, in order, in the
ranges of weight % listed in Table 10: water, polyurethane dispersion,
benzyl benzoate, dipropylene glycol butyl ether, tri-n-butyl citrate and
propylene glycol. The contents were then mixed at slow speeds until fully
dispersed. The speed was maintained at no more than 200-400 rpm. There
was no Hegman grind to measure in this formula. Once blending was
achieved, mixing speed was reduced until the pot was just mixing the raw
materials and continued for 10-15 minutes.

[0168] During the letdown stage, 2,4,7,9-tetramethyl-5-decyne-4,7-diol,
and ethylene glycol were added to the pot. The speed was maintained to
mix the material. After less than 5-10 minutes, an emulsion of
organo-modified polysiloxanes and α-octadecyl-ω-hydroxy
poly(oxy-1,2-ethanediyl), was added to the pot. The speed was maintained
to mix the material. After less than 5-10 minutes, nonionic polyethylene
wax was added to the pot. The speed was maintained to mix the material.
After 15-20 minutes the product was packaged. The composition of the
formulation is described in Table 10.

[0169] During the grind stage, to the pot were added, in order, in the
ranges of weight % listed in Table 11: water, propylene glycol,
polypropylene glycol, polysiloxanes, polycarboxylate-sodium salt,
alkanes, 2-butoxyethanol and ethoxylated alkylphenol. The contents were
then mixed at slow speeds until fully dispersed. The speed was maintained
at no more than 100-200 rpm. Titanium dioxide, aluminum hydroxide,
amorphous silica and water were added to the mixture in the pot, while
increasing the speed to achieve a good vortex. Final RPM settings were
between 2,000-3,000 rpm. The speed was adjusted until maximum shear was
obtained with minimal integration of air and mixed for 10-15 minutes, or
a Hegman of 5-6. After ascertaining that there were no chunks, the speed
was increased to achieve sufficient vortex. A sufficient RPM was
maintained while keeping the temperature in the pot below 95-110°
F. Hegman at this point was at least a 7. Once Hegman was achieved,
mixing speed was reduced until the pot was just mixing the raw materials
and continued for 10-15 minutes.

[0170] During the letdown stage, polyurethane/acrylic mixture,
1-ethylpyrrolidin-2-one and 2-(2-butoxyethoxy) ethanol were added to the
grind mixture. The speed was maintained to mix the material. After less
than 5-10 minutes, benzoate esters were added to the pot. The speed was
maintained to mix the material. After less than 5-10 minutes,
polyurethane resin was added to the pot. The speed was maintained to mix
the material. After less than 5-10 minutes, polyurethane resin and
enzymatically modified starch were added to the pot. The speed was
maintained to mix the material. After 15-20 minutes the product was
packaged. The composition of the formulation is described in Table 11.

[0171] During the grind stage, to the pot were added, in order, in the
ranges of weight % listed in Table 12: water, propylene glycol, xylene,
polypropylene glycol, polysiloxanes, polycarboxylate-sodium salt,
alkanes, 2-butoxyethanol and ethoxylated alkylphenol. The contents were
then mixed at slow speeds until fully dispersed. The speed was maintained
at no more than 100-200 rpm. Titanium dioxide, aluminum hydroxide,
amorphous silica and water were added to the mixture in the pot, while
increasing the speed to achieve a good vortex. Final RPM settings were
between 2,000-3,000 rpm. The speed was adjusted until maximum shear was
obtained with minimal integration of air and mixed for 10-15 minutes, or
a Hegman of 5-6. After ascertaining that there were no chunks, the speed
was increased to achieve sufficient vortex. A sufficient RPM was
maintained while keeping the temperature in the pot below 95-110°
F. Hegman at this point was at least a 7. Once Hegman was achieved,
mixing speed was reduced until the pot was just mixing the raw materials
and continued for 10-15 minutes.

[0172] During the letdown stage, acrylic copolymer emulsion was added to
the grind mixture. The speed was maintained to mix the material. After
less than 5-10 minutes, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate
was added to the pot. The speed was maintained to mix the material. After
less than 5-10 minutes, polyurethane resin was added to the pot. The
speed was maintained to mix the material. After less than 5-10 minutes,
polyurethane resin and enzymatically modified starch were added to the
pot. The speed was maintained to mix the material. After 15-20 minutes
the product was packaged. The composition of the formulation is described
in Table 12.

[0173] During the grind stage, to the pot were added, in order, in the
ranges of weight % listed in Table 13: water, xylene, polypropylene
glycol, polysiloxanes, and functionalized polyacrylate copolymers. The
contents were then mixed at slow speeds until fully dispersed. The speed
was maintained at no more than 100-200 rpm. Titanium dioxide, aluminum
hydroxide, amorphous silica and water were added to the mixture in the
pot, while increasing the speed to achieve a good vortex. Final RPM
settings were between 2,000-3,000 rpm. The speed was adjusted until
maximum shear was obtained with minimal integration of air and mixed for
10-15 minutes, or a Hegman of 5-6. After ascertaining that there were no
chunks, the speed was increased to achieve sufficient vortex. A
sufficient RPM was maintained while keeping the temperature in the pot
below 95-110° F. Hegman at this point was at least a 7. Once
Hegman was achieved, mixing speed was reduced until the pot was just
mixing the raw materials and continued for 10-15 minutes.

[0174] During the letdown stage, 2-amino-2-methyl-1-propanol and
2-(methylamino)-2-methyl-1-propanol were added to the grind mixture. The
speed was maintained to mix the material. After less than 5-10 minutes,
epoxy based styrene-acrylic copolymer was added to the pot. The speed was
maintained to mix the material. After less than 5-10 minutes, dipropylene
glycol monomethyl ether was added to the pot. The speed was maintained to
mix the material. After less than 5-10 minutes,
2,2,4-trimethyl-1,3-pentanediol monoisobutyrate was added to the pot. The
speed was maintained to mix the material. After less than 5-10 minutes,
polyurethane resin was added to the pot. The speed was maintained to mix
the material. After less than 5-10 minutes, polyurethane resin and
2-butoxyethanol were added to the pot. The speed was maintained to mix
the material. After 15-20 minutes the product was packaged. The
composition of the formulation is described in Table 13.

Quantitative Determination of the Erasable Characteristics of the
Writable-Erasable Surface

[0175] The color stimulus, which is the radiation from the colored object
that produces the perception of that color, can be measured. Color
perception is affected not only by the spectral make up of the object,
but also the light source under which it is viewed. If the spectral
distribution of the light source and the relative spectral reflectance of
the object are known, then the spectral composition reaching the eye of
an observer with normal vision from the object illuminated by that source
can be calculated. The Commission Internationale de L'Eclairage (CIE) has
set up procedures for calculation of the color differences in a CIELAB
color space. The X-Rite Sp-62 Spectrophotometer can be used to take the
color readings and it calculates these values automatically. The values
can then be recorded. The changes can then be calculated according to
ASTM Test Method D2244, as differences in the L*, a*, and b* values,
where the direction of the color difference is described by the magnitude
and the algebraic signs of the components, ΔL*, Δa*,
Δb*. The values are then calculated as follows:

ΔL*=L*1-L*0 (1)

Δn*=a*1-a*0 (2)

Δb*=b*1-b*0 (3)

where L*0, a*0, b*0 refers to the reference, and L*1,
a*1, b*1, refers to the test specimen. Table 14 shows the
magnitude and direction of each color value and what color change occurs.

By choosing one sample to be the reference point, the change in color
from this reference point is called the color difference (ΔE),
which is calculated from the equation:

ΔE=[(ΔL*)2+(Δa*)2+(Δb*)2]1/2
(4)

Example 15

Determination of Erasable Characteristics of a Writable-Erasable Surface

[0176] The nature of visual change (erasable characteristics) on the
writable-erasable surface can be evaluated by the visual change perceived
after the surface has been marked followed by erasing the marking. It can
be characterized by the leave behind which can be determined after 1 or 2
passes by the eraser to erase the marking: the markings may seem to stick
to the surface and they might erase as in streaks or might be spotty. The
quality of the surface can also be measured by the dirtiness which can be
determined after one pass with the eraser over the marked area, a faint
to dark cloud might be left from the eraser, like smearing of the marking
due to the eraser. Both "leave behind" and "dirtiness" can be measured on
a scale of zero to ten based on the degree to which the marking material
can be removed from the surface. The lower number indicates a better
surface performance.

Example 16

Application of the Coating

[0177] The application is performed in a clean, dustless environment.
Prior to installation, the ambient temperature within the application
site is maintained at not less than 45° F. for a minimum of 24
hours and proper ventilation of application areas is ascertained to
minimize odors in vicinity of application. The surface of the substrate
to be painted on is primed, using a non-tinted PVA or vinyl acrylic
interior latex primer, until the color of the existing surface does not
show through. The primer is allowed to dry completely according to
manufacturer's recommendation. The surface is painted in approximately 2
foot wide sections by working from one end to the other. Each section is
completed before painting the next section. A wet edge is maintained to
avoid lap marks. A single coat is applied using foam roller covers. The
equipment is cleaned with acetone or denatured alcohol. The coating is
allowed to cure for 1 week, at room temperature, to form the
writable-erasable surface.

[0178] The writable-erasable surface can be maintained by daily erasure
and cleaning with a standard dry-erase eraser or a dry cloth. For
periodic and more thorough cleaning, a damp cloth may be used.

[0179] If it is desired to clear the writable-erasable surface or recoat
any damaged surface, the original surface is deglossed by sanding the
surface and priming before application of the dry erase coating.

OTHER IMPLEMENTATIONS

[0180] A number of implementations have been described. Nevertheless, it
will be understood that various modifications can be made without
departing from the spirit and scope of the disclosure. Accordingly, other
implementations are within the scope of the following claims.

[0181] For example, while rollers have been described for applying the
materials, brushes, pre-loaded applicators, or sprayers can be used. When
sprayers are used, the precursor materials can be first mixed and then
sprayed onto a substrate, or the precursor materials can each be sprayed
from separate nozzle outlet, the mixing of the precursors occurring in
flight toward the substrate and/or on the substrate.

[0182] While whiteboards and coated walls have been described, the
coatings can be applied to other forms. For example, referring now to
FIG. 3, any of the materials described herein can be applied to a
continuous sheet of material, such as paper, to provide a product 50 that
includes a substrate 52 and a coating 54 extending upon the substrate 52.
As shown in FIG. 3, the product 50 can be conveniently stored in a roll
form. If desired, product 50 can be cut, e.g., along a transverse line
60, to provide individual sheets 70 of material. Referring now to FIG. 4,
sheets 70 can be fashioned into a product 80 in tablet form using
fasteners 82. If desired, the assembled sheets can have perforations 86,
allowing sheets to be torn from the tablet and used as a mobile
writable-erasable product.

[0183] Blends of polyurethane materials and any one of, some of, or all of
epoxy resins, acrylic resins described herein can be used to make the
coatings having the writable-erasable surface.

[0184] Other water-based materials may be used alone, or in combination
with other water-based materials described herein, such as polyurethane
materials. For example, epoxy resins in a water-based carrier may be
utilized. These epoxy resins may be used in conjunction with various
crosslinkers and/or additives described herein. For example, the
crosslinkers can be a moiety that includes a plurality of amino groups,
thiol groups, hydroxyl groups or mixtures of such groups. Water-based
epoxy resins are commercially available under the name Enducryl® from
Epoxy Systems, Inc.

[0185] The first and second components can be applied to the substrate,
e.g., by concurrently spraying the components so that they mix in flight
and/or on the substrate, and then optionally applying a crosslinking
promoter, such as an acid, to the mixed first and second components,
e.g., in the form of a solution. In still other implementations, a
crosslinking promoter is first applied to the substrate, and then the
first and second components are applied to the substrate having the
crosslinking promoter.

[0186] The first and second components can be mixed, e.g., by alternately
adding the desired, pre-determined quantities of the components from a
large drum to a paint bucket, mixing, and then applying the coating on a
substrate. The advantage of this method is that the pot life of the
components are preserved without wasting the components.

[0187] Still other implementations are within the scope of the following
claims.